Hyperbranched copolymer comprising monomers of choice, a composition, and a cosmetic method

ABSTRACT

Disclosed is a hyperbranched copolymer comprising at least two polymeric branches, which may be identical or different, each comprising at least one at least trifunctional branch point, wherein a first polymeric branch comprises at least one first monomer chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, a second polymeric branch comprises at least one second monomer chose from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate. Also disclosed is a cosmetic or pharmaceutical composition, for example, a dermatological composition, comprising said hyperbranched copolymer. Further disclosed is a cosmetic method of making up or caring for keratin materials, comprising applying to said materials a cosmetic composition comprising said hyperbranched copolymer.

This application claims benefit of U.S. Provisional Application No.60/613,507, filed Sep. 28, 2004, the contents of which are incorporatedherein by reference. This application also claims benefit of priorityunder 35 U.S.C. § 119 to French Patent Application No. 04 08373, filedJul. 29, 2004, the contents of which are also incorporated by reference.

The present disclosure pertains to new hyperbranched copolymers and alsoto compositions, for example, cosmetic or pharmaceutical compositions,and further, for example, topical dermatological compositions,comprising said copolymers; it also relates to the use of thesecopolymers, for example, in the field of making up and/or caring forkeratin materials, for example, the skin of the body or of the face, andthe lips.

Within the field of cosmetology a frequent aim is to have compositionsavailable that allow a deposit, for example, an adhesive or film-formingdeposit, to be obtained on the keratin materials in question, such asthe skin, lips, hair, eyelashes or nails.

For example, these compositions are able to provide color (makeup orhair coloring compositions), gloss or mattness (skin makeup or carecompositions), physical properties such as shaping, (hair compositions,for example, styling compositions), and properties of care or protection(care compositions, for example moisturizing or UV-protectioncompositions).

The aim is generally that the cosmetic deposit should have goodpersistence and staying power over time and also good adhesion to thesubstrate. For example, it is desirable for this deposit to be able towithstand mechanical attacks such as rubbing and transfer by contactwith another object, and also to withstand water, perspiration, tears,rain, sebum, and oils. This is particularly true in the makeup field,for example, in the sector of lipsticks, where there is a desire forprolonged colorfastness and gloss staying power, and for transferresistance of the color; within the sector of foundations, eyeshadowsand powders, where there is a desire for the color provided to be fast,with the mattness of the initial makeup being maintained for as long aspossible despite the secretion of sebum and perspiration, and also fortransfer resistance. Moreover, makeup compositions must be comfortableto wear and must not have too sticky a texture.

In order to reconcile the entirety of these properties, which are oftenmutually contradictory, within a single composition, it is possible toemploy a blend of two or more polymers, very different in chemicalnature, each polymer providing one of the desired characteristics.Nevertheless, the use of a blend of polymers having different chemicalnatures, not necessarily compatible with one another, may give rise toproblems of separation within the composition.

The use of random polymers, for example of conventional acrylic polymersobtained by conventional free-radical polymerization by statisticalmixing of monomers, does not allow these problems to be solvedsatisfactorily. The reason for this is that the random polymers knownpreviously exhibit a dispersity in terms of composition of the polymericchains, which also leads to separation of the polymers within theformula.

Also known are hyperbranched polymers, which have been proposed for usein hair cosmetology, in PCT Application No. WO 01/96429; thesehyperbranched polymers are prepared from a first type of acrylicmonomers and from branching monomers possessing two polymerizablefunctions with different reactivities, to give polymers comprisingpendant allylic units, which can be polymerized subsequently in thepresence of a second type of acrylic monomers.

However, the polymers described in PCT Application No. WO 01/96429 aresoluble in aqueous media and are difficult to formulate in thelipophilic media that are generally employed in cosmetology, such asoily media or solvents. Certain cosmetic makeup compositions, though,such as lipsticks and foundations, very generally comprise a fattyphase.

The aim of at least one embodiment of the present disclosure is toovercome at least one drawback discussed above by providing new,specific hyperbranched copolymers which in at least one embodimentevades the problems of separation within the formula while at the sametime allowing the desired cosmetic properties to be provided. In atleast one embodiment, these polymers are easy to formulate in thelipophilic media of cosmetic compositions.

An embodiment of the present invention is a hyperbranched copolymercomprising at least two, for example, three, polymeric branches, whichmay be identical or different, each comprising at least one at leasttrifunctional branch point, wherein a first polymeric branch comprisesat least one first monomer chosen from isobornyl acrylate, isobornylmethacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexylacrylate, a second polymeric branch comprises at least one secondmonomer chose from isobornyl acrylate, isobornyl methacrylate, isobutylacrylate, isobutyl methacrylate and 2-ethylhexyl acrylate. Anotherembodiment is a cosmetic or pharmaceutical composition, for example, adermatological composition, comprising said copolymer.

In an embodiment, the polymers according to the invention may have theadvantage of allowing a film to be obtained which may be flexible andnot at all sticky.

As used herein, “Hyperbranched polymers” means polymers comprising atleast two, for example three, polymeric branches, forming either themain branch or a secondary branch, and each comprising at least one atleast trifunctional branch point, which may be identical or different,and which is able to form at least two at least trifunctional branchpoints, different from and independent of one another. Each branch pointmay be, for example, arranged in the interior of at least one chain.

The branches may be, for example, connected to one another by apolyfunctional compound, for example, a compound as defined later or inthe description, which, for example, has different reactivities.

As used herein, “trifunctional branch point” means the junction pointbetween three polymer branches, of which at least two branches may bedifferent in chemical constitution and/or structure. For example,certain branches may be hydrophilic, i.e. may predominantly containhydrophilic monomers, and other branches may be hydrophobic, i.e., maypredominantly contain hydrophobic monomers. Further branches mayadditionally form a random polymer or a block polymer.

As used herein, “at least trifunctional branch” means the junctionpoints between at least three polymeric branches, for example npolymeric branches, of which n-1 branches at least are different inchemical constitution and/or structure.

As used herein, “chain interior” means the atoms situated within thepolymeric chain, to the exclusion of the atoms forming the two ends ofthis chain.

As used herein, “main branch” means the branch or polymeric sequencecomprising the greatest percentage by weight of monomer(s).

Branches which are not main branches are called “secondary branches”.

As used herein, “hyperbranched polymer” does not encompass, for example:

-   branched or graft polymers, i.e. polymers composed of a main chain    having multiple trifunctional branch points from each of which a    linear side-chain emanates, wherein the side-chains may be composed    of at least one block, these side-chains being identical or    different in nature to or from the main chain, such as, for example,    those described in document European Patent No. EP815848, relating    to copolymers having a carbon/fluorine skeleton with a Tg ranging    from 0 and 30° C. and to rigid grafts having a Tg of more than 25°    C., or in PCT Application No. WO 97/35541, relating to copolymers    having a rigid, hydrophilic vinyl/acrylic skeleton and flexible,    hydrophobic grafts;-   comb polymers (specific case of graft polymers), i.e. polymers    composed of a main chain having multiple trifunctional branch points    from each of which a linear side-chain emanates (Glossary of basic    terms in polymer science/IUPAC/1996), the branch points being    situated at regular intervals;-   star polymers, i.e. those polymers all of whose branch points are    located at a single point.

In one embodiment, the at least one hyperbranched polymers comprise atleast two polymeric branches, forming either the main branch or asecondary branch, and each comprising at least one trifunctional branchpoint, different from and independent of one another, which may form atleast two trifunctional branch points, different from and independent ofone another, each branch point being arranged, for example, in theinterior of at least one chain.

As a non-limiting example, the copolymers according to the invention maybe considered as capable of illustration by the following scheme:

wherein A and B are chosen from the monomers of choice and/or additionalmonomers, as defined below, m and n being their degree ofpolymerization, and X is chosen from the trifunctional branching pointwhich is present on each of the branches and may originate from apolyfunctional compound as defined below.

In an embodiment, the copolymers according to the invention may have theadvantage of being easy to employ in organic cosmetic media, forexample, media comprising lipophilic solvents and/or cosmetic oils,while retaining advantageous rheological properties.

For example, the copolymers according to the invention may exhibit goodsolubility in solvents, for example, lipophilic solvents, and/or incosmetic oils.

As used herein, when a polymer is “soluble” in a medium means a polymerwhich does not form a precipitate but may, for example, form a clearsolution in said medium at 25° C.

For example, the copolymer according to the disclosure is soluble at aconcentration of at least 3% by weight in isododecane at 25° C. and 1atm, for example, in a concentration of at least 5% by weight, further,for example, at least 10% by weight.

The copolymers according to the invention are therefore hyperbranchedcopolymers, i.e. copolymers comprising at least two, for example, atleast three, polymeric branches, which can form either the main branchor a secondary branch, and each comprising at least one at leasttrifunctional branch point different from and independent of oneanother, for example, so as to form at least two at least trifunctionalbranch points, different from and independent of one another.

For example, the hyperbranched copolymers according to the disclosurecontain units derived from at least one ethylenic monomer capable, forexample, of undergoing free-radical polymerization, to form branches ofsaid polymer, wherein each branch is in the form of a polymeric sequenceof homopolymer kind or of random, alternating, block or gradientcopolymer kind; for example, each branch is in the form of a homopolymeror of a linear random copolymer.

The copolymers according to the disclosure contain at least one firstbranch or polymeric sequence comprising at least one first monomer ofchoice, and at least one second sequence (or second branch) comprisingat least one second monomer of choice, which may be identical to ordifferent from said first monomer of choice.

As used herein, “monomer of choice” means monomers selected from thefollowing list: isobornyl acrylate, isobornyl methacrylate, isobutylacrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

Each branch or sequence may of course comprise a mixture of monomers ofchoice, it being possible for each branch to have a different chemicalcomposition and/or structure.

In one embodiment are copolymers wherein the main branch is in the formof a homopolymer or random copolymer comprising 80% to 100% by weight,for example, 100% by weight, relative to the weight of the branch, ofmonomer(s) of choice.

In another embodiment are copolymers wherein the secondary branch orbranches are in the form of a homopolymer or a randomcopolymer-comprising 80%-100% by weight, for example, 100% by weight,relative to the weight of the branch, of at least one monomer of choice.

The copolymer according to the disclosure may therefore comprise a firstbranch which will comprise a first monomer of choice, or else a mixtureof at least two monomers of choice, for example, three monomers ofchoice, or else a mixture of one or two monomers of choice with at leastone additional monomers as defined below.

The copolymer according to the disclosure may also comprise at least onesecond branch which may comprise a monomer of choice which is differentfrom said first monomer of choice or identical to said first monomer ofchoice, which may also be alone or in a mixture with at least one othermonomers of choice, and/or with at least one additional monomers asdefined below.

For example, the total amount of monomers selected from the monomers ofchoice in the final copolymer ranges from, for example, 50% to 100% byweight, for example, from 60% to 98% by weight, further, for example,from 70% to 97% by weight, even further, for example, from 80% to 96% byweight, and even further, for example, from 90% to 95% by weight, ofmonomers of choice relative to the total weight of monomers present inthe final copolymer.

The copolymer according to the disclosure may comprise, for example, 25%to 75% by weight, for example 30% to 70% by weight, of a first monomerof choice, which is present in a first branch, and 25% to 75% by weight,for example, 30% to 70% by weight, of a second monomer of choice, whichmay be present in the same branch or in another branch, the percentagesbeing given relative to the total weight of monomers present in thefinal copolymer.

It may further comprise, optionally, from 1% to 40% by weight, forexample, from 5% to 30% by weight, further, for example, 10% to 25% byweight, relative to the weight of the final copolymer, of at least onethird monomer selected from the monomers of choice, the percentagesbeing given relative to the total weight of monomers present in thefinal copolymer.

For example, copolymers may be chosen from—irrespective of whether inthe same branch or in different branches—the following monomercombinations:

-   isobornyl acrylate and isobornyl methacrylate;-   isobornyl acrylate and isobutyl acrylate;-   isobornyl acrylate and isobutyl methacrylate;-   isobornyl acrylate and 2-ethylhexyl acrylate;-   isobornyl methacrylate and isobutyl acrylate;-   isobornyl methacrylate and isobutyl methacrylate;-   isobornyl methacrylate and 2-ethylhexyl acrylate;-   isobornyl acrylate, isobornyl methacrylate and 2-ethylhexyl    acrylate;-   isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate;-   isobornyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate;-   isobornyl acrylate, isobutyl methacrylate and isobutyl acrylate; and-   isobornyl methacrylate, isobutyl methacrylate and isobutyl acrylate.

For example, the copolymers may comprise:

-   isobornyl acrylate in the main branches and isobutyl acrylate in the    secondary branches;-   isobornyl acrylate in the main branches and 2-ethylhexyl acrylate in    the secondary branches;-   isobornyl methacrylate in the main branches and isobutyl acrylate in    the secondary branches;-   isobornyl methacrylate in the main branches and 2-ethylhexyl    acrylate in the secondary branches;-   isobornyl acrylate and isobornyl methacrylate in the main branches    and isobutyl acrylate in the secondary branches;-   isobornyl acrylate and isobornyl methacrylate in the main branches    and 2-ethylhexyl acrylate in the secondary branches;-   isobornyl acrylate and isobutyl methacrylate in the main branches    and isobutyl acrylate in the secondary branches;-   isobornyl acrylate and isobutyl methacrylate in the main branches    and 2-ethylhexyl acrylate in the secondary branches;-   isobornyl methacrylate and isobutyl methacrylate in the main    branches and isobutyl acrylate in the secondary branches; or-   isobornyl methacrylate and isobutyl methacrylate in the main    branches and 2-ethylhexyl acrylate in the secondary branches.

The copolymer according to the disclosure may further comprise at leastone additional monomer other than those selected from the monomers ofchoice.

This at least one additional monomer, or mixture of additional monomers,may be present in an amount ranging from 0 to 50% by weight, forexample, from 2% to 40% by weight, further, for example, from 3% to 30%by weight, even further, for example, from 4% to 20% by weight, and evenfurther, for example, from 5% to 10% by weight, relative to the totalweight of monomers present in the final copolymer.

This at least one additional monomer may be selected, alone or in amixture, from the following monomers, and also their salts, with theexception, of course, of the abovementioned monomers of choice:

-   (i) (meth)acrylates of formula CH₂═CHCOOR or CH₂═C(CH₃)COOR wherein    R is chosen from:

a linear or branched alkyl group comprising 1 to 30 carbon atoms,wherein said alykl is optionally intercalated with at least oneheteroatom selected from O, N, S and P, and/or wherein said alkyl groupis optionally substituted by at least one substituent selected from —OH,halogen atoms (Cl, Br, I and F), —NR4R5, where R4 and R5, which may beidentical or different, are chosen from hydrogen or a C₁ to C₆ linear orbranched alkyl groups and phenyl groups; and polyoxyalkylene groups, forexample, polyoxyethylene and/or polyoxypropylene, consisting of therepetition of 5 to 30 oxyalkylene units;

a C₃ to C₁₂ cycloalkyl group, said cycloalkyl group being able tocontain, in its chain, at least one heteroatom selected from O, N, Sand/or P, and/or to be optionally substituted by at least onesubstituent selected from —OH and halogen atoms (Cl, Br, I and F);

a C₄ to C₂₀ aryl or C₅ to C₃₀ aralkyl group (with a C₁ to C₈ alkylgroup); for example, R may be a methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl,isooctyl, isodecyl, dodecyl, cyclohexyl, t-butylcyclohexyl, stearyl,2-ethylperfluorohexyl, 2-hydroxyethyl, 2-hydroxybutyl, 2-hydroxypropyl,methoxyethyl, ethoxyethyl, methoxypropyl, isobornyl, phenyl,2-phenylethyl, t-butylbenzyl, benzyl, furfurylmethyl ortetrahydrofurfurylmethyl group, a methoxy-polyoxyethylene (orPOE-methyl) group; a POE-behenyl or trifluoroethyl group; or adimethylaminoethyl, diethylaminoethyl or dimethylaminopropyl group;

-   (ii) (meth)acrylamides of formula CH₂═CHCONR4R5 or CH₂═C(CH₃)CONR4R5    wherein R4 and R5, which may be identical or different, are chosen    from-   a) a hydrogen atom;-   b) a linear or branched alkyl group comprising 1 to 18 carbon atoms,    wherein said alkyl is optionally intercalated with at least one    heteroatom selected from O, N, S and P; wherein said alkyl group may    be optionally substituted by at least one substituent selected from    hydroxyl groups, halogen atoms (Cl, Br, I and F) and Si(R4R5),    wherein R4 and R5, which may be identical or different, are chosen    from a C₁ to C₆ alkyl groups and phenyl groups; for example, a    methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl,    hexyl, isohexyl, cyclohexyl, ethylhexyl, octyl, isooctyl, decyl,    isodecyl, cyclodecyl, dodecyl, cyclododecyl, isononyl, lauryl,    t-butylcyclohexyl or stearyl group; a 2-ethylperfluorohexyl group;    or a C₁₋₄ hydroxyalkyl group such as 2-hydroxyethyl, 2-hydroxybutyl    and 2-hydroxypropyl; or a C₁₋₄ alkoxy-C1-4 alkyl group such as    methoxyethyl, ethoxyethyl and methoxypropyl,-   c) a C₃ to C₁₂ cycloalkyl group, such as the isobornyl group, or a    heterocycloalkyl group (with alkyl of 1 to 4 carbon atoms), such as    furfurylmethyl or tetrahydrofurfurylmethyl,-   d) a C₄ to C₂₀ aryl group such as a phenyl group, and-   e) a C₅ to C₃₀ aralkyl group (with a C₁ to C₈ alkyl group) such as    2-phenylethyl, t-butylbenzyl or benzyl;-   (iii) ethylenically unsaturated monomers comprising at least one    carboxylic, phosphoric or sulphonic acid or anhydride function, such    as, for example, acrylic acid, methacrylic acid, crotonic acid,    maleic anhydride, itaconic acid, fumaric acid, maleic acid,    styrenesulphonic acid, vinylbenzoic acid, vinylphosphoric acid or    acrylamidopropanesulphonic acid; and the salts thereof;-   (iv) vinyl ethers of formula R6O—CH═CH₂ or vinyl esters of formula    R6-COO—CH═CH₂ wherein R6 is chosen from a linear or branched alkyl    groups comprising from 1 to 22 carbon atoms or a cyclic alkyl group    comprising from 3 to 6 carbon atoms and/or an aromatic group, for    example, benzene, anthracene or naphthalene;-   (v) vinyl compounds chosen from CH₂═CH—R9, CH₂═CH—CH₂—R9 or    CH₂═C(CH₃)═CH₂—R9 wherein R9 is a hydroxyl, halogen (Cl or F) or NH₂    group or a group OR10 wherein R10 is chosen from phenyl groups; C₁    to C₁₂ alkyl groups (the monomer is a vinyl or allyl ether);    acetamide groups (NHCOCH₃); OCOR11 wherein R11 is chosen from an    alkyl group of 2 to 12 carbons which is linear or branched (the    monomer is a vinyl or allyl ester); or a group selected from:

linear or branched alkyl groups of 1 to 18 carbon atoms, wherein saidalkyl is intercalated with at least one heteroatom selected from O, N, Sand P, wherein alkyl group is optionally substituted by at least onesubstituent selected from hydroxyl groups, halogen atoms (Cl, Br, I andF) and groups Si(R4R5), wherein R4 and R5, which may be identical ordifferent, are chosen from C₁ to C₆ alkyl groups or phenyl groups;

C₃ to C₁₂ cycloalkyl groups such as isobornyl or cyclohexane,

C₃ to C₂₀ aryl groups such as phenyl,

C₄ to C₃₀ aralkyl groups (with a C1 to C8 alkyl group) such as2-phenylethyl or benzyl,

4- to 12-membered heterocyclic groups comprising at least one heteroatomselected from O, N and S, the ring being aromatic or non-aromatic, and

heterocycloalkyl groups a C₁ to C₄ alkyl group, such as furfurylmethylor tetrahydrofurfurylmethyl;

-   (vi) styrene and its derivatives, for example, methylstyrene,    chlorostyrene or chloromethylstyrene;-   (vii) ethylenically unsaturated monomers comprising at least one    silicon atoms, such as methacryloyloxypropyltrimethoxysiloxane and    methacryloyloxypropyltris(trimethylsiloxy)silane;-   and also their salts, and mixtures thereof.

Among these additional monomers non-limiting mention may be made ofmethyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclohexyl,methoxyethyl, ethoxyethyl, trifluoroethyl, dimethylaminoethyl,diethylaminoethyl, 2-hydroxypropyl and 2-hydroxyethyl (meth)acrylates;acrylic acid, methacrylic acid, (meth)acrylamide,methacryloyloxypropyltrimethoxy-silane,methacryloyloxypropyltris(trimethylsiloxy)silane; and also their salts;and mixtures thereof.

As additional monomers it is also possible to employ carbon or siliconemacromonomers having at least one polymerizable end group. This is anypolymer, for example, an oligomer, comprising at only one of its ends anend group, for example, a polymerizable end group, which during thepolymerization reaction is capable of reacting with the monomers inquestion to form the side-chains of the polymer; said end group may, forexample, be an ethylenically unsaturated group capable of undergoingfree-radical polymerization with the monomers making up the skeleton.Said macromonomer allows the side-chains of the copolymer to be formed.The polymerizable group of the macromonomer may, for example, be anethylenically unsaturated group capable of undergoing free-radicalpolymerization. Said polymerizable end group may, for example, be avinyl or (meth)acrylate group. Among the additional macromonomers whichcan be employed non-limiting mention may be made, for example, of thefollowing, alone or in a mixture, and also their salts:

-   (i) linear or branched C₈-C₂₂ alkyl (meth)acrylate homopolymers and    copolymers having a polymerizable end group selected from vinyl or    (meth)acrylate groups, among which non-limiting mention may be made    of poly(2-ethylhexyl acrylate) macromonomers having a    mono(meth)acrylate end group; poly(dodecyl acrylate) or poly(dodecyl    methacrylate) macromonomers having a mono(meth)acrylate end group;    and poly(stearyl acrylate) or poly(stearyl methacrylate)    macromonomers having a mono(meth)acrylate end group. Macromonomers    of this kind are described, for example, in European Patent Nos.    EP895467 and EP96459.-   (ii) polyolefins having an ethylenically unsaturated end group, for    example, those having a (meth)acrylate end group. As examples of    such polyolefins non-limiting mention may be made, for example, of    the following macromonomers, on the understanding that they have a    (meth)acrylate end group: polyethylene macromonomers, polypropylene    macromonomers, polyethylene/polypropylene copolymer macromonomers,    polyethylene/polybutylene copolymer macromonomers, polyisobutylene    macromonomers; polybutadiene macromonomers; polyisoprene    macromonomers; and poly(ethylene/butylene)-polyisoprene    macromonomers. Macromonomers of this kind are described, for    example, in U.S. Pat. No. 5,625,005, which mentions    ethylene/butylene and ethylene/propylene macromonomers having a    (meth)acrylate reactive end group. Non-limiting mention may be made,    for example, of poly(ethylene/butylene) methacrylate, such as that    sold under the name Kraton Liquid L-1253 by Kraton Polymers.-   (iii) polydimethylsiloxanes having a mono(meth)acrylate end group,    and for example, those of formula (IIa):    wherein:-   R₈ is chosen from a hydrogen atom and a methyl group; for example, a    methyl group;-   R₉ is chosen from linear or branched, for example, linear, divalent    hydrocarbon groups having 1 to 10 carbon atoms and optionally    comprising one or two ether bonds —O—; for example, ethylene,    propylene or butylene;-   R₁₀ is chosen from a linear or branched alkyl groups having 1 to 10    carbon atoms, for example, 2 to 8 carbon atoms; for example, methyl,    ethyl, propyl, butyl or pentyl;-   n is chosen from an integer ranging from 1 to 300, for example,    ranging from 3 to 200 and further, for example, ranging from 5 to    100.

As silicone macromonomers non-limiting mention may be made, for example,of monomethacryloyloxypropylpoly-dimethylsiloxanes, such as those soldunder the name PS560-K6 by UCT (United Chemical Technologies Inc.) orunder the name MCR-M17 by Gelest Inc.

Among the salts, non-limiting mention may be made of those obtained byneutralizing acid groups using mineral bases such as LiOH, NaOH, KOH,Ca(OH)₂, NH₄OH or Zn(OH)₂; or by an organic base such as a primary,secondary or tertiary alkylamine, for example, triethylamine orbutylamine. This primary, secondary, or tertiary alkylamine may compriseat least one nitrogen and/or oxygen atoms and may therefore comprise,for example, at least one alcohol functions; non-limiting mention may bemade, for example, of 2-amino-2-methylpropanol, triethanolamine and2-dimethylaminopropanol. Non-limiting mention may also be made of lysineor 3-(dimethylamino)propylamine.

Non-limiting mention may also be made of the salts of mineral acids,such as sulphuric acid, hydrochloric acid, hydrobromic acid, hydriodicacid, phosphoric acid and boric acid. Non-limiting mention may also bemade of the salts of organic acids, which may comprise at least onecarboxylic, sulphonic or phosphoric acid groups. These may be linear,branched or cyclic aliphatic acids or else aromatic acids. These acidsmay further comprise at least one heteroatom selected from O and N, inthe form for example of hydroxyl groups. Non-limiting mention may bemade, for example, of propionic acid, acetic acid, terephthalic acid,citric acid and tartaric acid.

In one embodiment, the copolymer according to the disclosure comprisesat least one “high-Tg” branch or polymeric sequence having a Tg greaterthan or equal to 20° C., for example, ranging from 20° C. to 150° C.,further, for example, from 30° C. to 120° C., and even further, forexample, from 40° C. to 100° C.

This branch is, for example, present in an amount greater than or equalto 50%, for example, from 55% to 95%, further, for example, from 60% to90% by weight, relative to the total weight of the polymer.

Likewise, for example, the copolymer according to the disclosurecomprises at least one “low-Tg” branch or sequence having a Tg ofstrictly lower than 20° C., for example, ranging from −150° C. to 19°C., further, for example, from −100° C. to 0° C., even further, forexample, from −80° C. to −5° C., and even further, for example, from−70° C. to −10° C.

This branch is, for example, present in an amount less than 50%, forexample, from 5% to 45%, further, for example, from 10% to 40% byweight, relative to the total weight of the polymer.

In another embodiment, the “high-Tg” branch comprises “high-Tg” monomersas defined below, which may be present in a proportion of 30% to 100% byweight, for example, 40% to 95% by weight, further, for example, from50% to 90% by weight, relative to the total weight of said branch.

In another embodiment, the “low-Tg” branch comprises “low-Tg” monomersas defined below, which may be present in a proportion of 30% to 100% byweight, for example, 40% to 95% by weight, further, for example, from50% to 90% by weight, relative to the total weight of said branch.

In another embodiment, copolymers are chosen such that the main branchis “high-Tg” and at least one of the secondary branches is “low-Tg”.

Furthermore, the copolymers according to the disclosure, for example,comprise at least one “high-Tg” monomer having a Tg greater than orequal to 20° C., for example, ranging from 20 to 150° C., further, forexample, ranging from 30 to 120° C., and even further, for example, from40 to 100° C., or a mixture of such monomers.

The at least one “high-Tg” monomer may be selected from the monomers ofchoice and/or from the additional monomers as described above.

The “high-Tg” monomer or monomers may be present in a proportion of 40%to 100% by weight, for example, 50% to 80% by weight, further, forexample, 55% to 70% by weight, relative to the total weight of monomerspresent in the copolymer.

In another embodiment, the copolymers according to the disclosure maytherefore likewise comprise at least one “low-Tg” monomer having a Tglower than than 20° C., for example, ranging from −150 to 19° C.,further, for example, from −100 to 0° C., even further, ranging from −80to −5° C., and even further, for example, from −70° C. to −10° C., or amixture of such monomers, said monomer or monomers being present in aproportion of 0 to 60% by weight, for example, from 20% to 50% byweight, further, for example, from 30% to 45% by weight, relative to thetotal weight of monomers present in the copolymer.

The at least one “low-Tg” monomer may be selected from the monomers ofchoice and/or from the additional monomers as described above.

By way of information it is noted that isobornyl acrylate has a Tg of94° C., isobornyl methacrylate a Tg of 110° C., and isobutylmethacrylate a Tg of 53° C., and they are all therefore “high-Tg”monomers, with a Tg of more than 20° C., whereas isobutyl acrylate has aTg of −24° C. and 2-ethylhexyl acrylate has a Tg of −50° C., and theyare therefore “low-Tg” monomers, with a Tg less than 20° C.

As used herein, “Tg monomer” means those monomers whose homopolymer hassuch a Tg. In the present disclosure the Tg (or glass transitiontemperatures) are theoretical Tg determined from the theoretical Tg ofthe constituent monomers of each of the sequences, and may be found in areference manual such as the Polymer Handbook, 3rd ed. 1989, John Wiley,in accordance with the following relationship, known as Fox's law:$\frac{1}{Tg} = {\sum\limits_{i}\left( \frac{\varpi\quad i}{Tgi} \right)}$ω_(i) being the mass fraction of the monomer i in the sequence inquestion and Tgi being the glass transition temperature of thehomopolymer of the monomer i (in kelvins).

In another embodiment, the copolymer according to the disclosurecomprises at least one lipophilic monomer, which may be selected fromthe monomers of choice and/or from the additional monomers, and whichmay be present in a proportion of 40% to 100% by weight, for example,50% to 80% by weight, further, for example, 55% to 70% by weight,relative to the total weight of monomers present in the copolymer.

In another embodiment, the copolymer according to the disclosure maycomprise at least one hydrophilic monomers, which may be selected fromthe monomers of choice and/or from the additional monomers and which maybe present in a proportion of 0 to 60% by weight, for example, 20% to50% by weight, further, for example, 30% to 45% by weight, relative tothe total weight of monomers present in the copolymer.

The copolymer according to the disclosure, for example, comprises 100%by weight of lipophilic monomers, which may be selected from themonomers of choice and/or from the additional monomers.

In another embodiment, the copolymer according to the disclosure ischosen from copolymers wherein the main branch is lipophilic, and in afurther embodiment a copolymer wherein the entirety of the branches,both main and secondary, are lipophilic.

By way of information it will be noted that isobornyl acrylate,isobornyl methacrylate, isobutyl methacrylate, isobutyl acrylate and2-ethylhexyl acrylate are lipophilic.

As used herein, a lipophilic monomer means any non-hydrophilic monomer.

As used herein, a hydrophilic monomer means any monomer whosehomopolymer is water-soluble, i.e. does not form a precipitate, butinstead forms, for example, a clear solution, in water, at 25° C., at 1atm and at a concentration of at least 1% by weight.

The skilled person will be able to select the monomers and their amountsas a function of the desired result, based on his or her generalknowledge, for example, on the relative reactivity of each monomer, onits Tg and on its lipophilicity. For example, he or she will select themonomers and their amount, and also the solvent medium, so as to give acopolymer which is soluble in said solvent medium.

In one embodiment, when the copolymer according to the disclosurecomprises acrylic acid and/or methacrylic acid, said monomers, forexample, may be present in a maximum amount of 20% by weight, forexample, an amount less than 15% by weight, for example, less than 10%by weight, relative to the total weight of monomers present in thecopolymer, so as to preserve its lipophilicity to the final copolymer.

In an embodiment, the number-average molecular mass of the copolymeraccording to the disclosure ranges from 2000 g/mol to 1 500 000 g/mol,for example, from 5500 g/mol to 1 000 000 g/mol, and further, forexample, from 6000 g/mol to 900 000 g/mol.

The weight-average (Mw) and number-average (Mn) molecular masses aredetermined by liquid gel-permeation chromatography (GPC), with THF aseluent, a calibration curve drawn up with linear polystyrene standards,and a refractometric detector.

The hyperbranched copolymers according to the disclosure may be obtainedfrom polymerization processes which are themselves known to the personskilled in the art.

Non-limiting mention may be made of a process comprising at least onestep comprising a free-radical polymerization in the presence of apolyfunctional compound.

Thus it is possible to react:

-   the ethylenic monomer or monomers envisaged for forming the    copolymer, or, for example, some of them, namely the monomer or    monomers of choice and/or additional monomer or monomers, as defined    above; and-   at least one polyfunctional compound, i.e. a compound comprising at    least two polymerizable functional groups or unsaturations, this    compound also being called a “chain extender” and defined below.

The reaction can be performed in two steps, the first step comprisingcopolymerizing the monomers envisaged for forming the main branch, inthe presence of a small amount of polyfunctional compound; for example,the reactivity of the functional groups of said polyfunctional compoundis such that the monomers envisaged for forming the main branch willreact preferentially with a first functional group,.leaving at least oneof the other functional groups unreacted.

In a second step, the monomers capable of forming the other branches canbe added, and will react preferentially with the unreacted functionalgroup of the polyfunctional compound, so as to form the hyperbranchedcopolymer. In this second step it is possible to add furtherpolyfunctional compound.

For example, the functions of the polyfunctional compound exhibitdifferent reactivities. For example, the polyfunctional compound maycomprise a (meth)acrylate function, which will polymerize rapidly, andan allylic function, which will polymerize more slowly.

As an example of a polyfunctional compound non-limiting mention may bemade, for example, of the compounds of formula (I) below:

wherein:

-   R_(a) and R_(c), which may be identical or different, each are    chosen from hydrogen and linear or branched alkyl radicals having 1    to 22 carbon atoms, for example, 1 to 3 carbon atoms; for example,    R_(a) may be a hydrogen atom; for example, R_(c) may be a methyl    radical;-   R_(b) is chosen from linear or branched divalent alkylene groups    having 1 to 22 carbon atoms, divalent cycloalkylene groups having 3    to 6 carbon atoms, divalent arylene groups having 6 to 18 carbon    atoms, and divalent alkarylene group having 7 to 24 carbon atoms;    for example, R_(b) is a methylene group;-   m and n independently of one another are 1, 2, 3 or 4 and are such    that the sum m+n is greater than or equal to 2; for example, m=n=1.

A polyfunctional compound or chain extender may, for example, be chosenfrom allyl (meth)acrylates, for example, allyl methacrylate.

Said polyfunctional compound may be used in an amount 0.05% to 15% byweight, for example, from 0.1% to 10% by weight, further for example,from 0.5% to 5% by weight of compound relative to the total weight ofthe final copolymer.

Dislcosed herein is a copolymer obtainable by a process comprising:

-   a first step comprising the free-radical polymerization in the    presence of at least one polyfunctional compound comprising at least    two polymerizable functional groups, some of the monomers envisaged,    selected from the monomer or monomers of choice and/or the    additional monomer or monomers, as defined above; and-   a second step comprising the free-radical polymerization of the    envisaged monomers, selected from the monomer or monomers of choice    and/or the additional monomer or monomers, as defined above,    optionally in the presence of a polyfunctional compound.

Hyperbranched copolymers may also be synthesized by reacting:

-   the free-radically polymerizable ethylenic monomer or monomers    envisaged, and-   compounds comprising at least one unsaturation and at least one site    capable of initiating the polymerization, following activation by    temperature, by UV radiation or by any mechanism other than that of    polymerization of the unsaturation; these compounds therefore    comprise both a site capable of promoting chain propagation, i.e. a    site comprising a double bond, and a site A capable of initiating    the chains.

This method is called “self-condensing vinyl polymerization”. It isdescribed in the work “Chimie et physico-chimie des polymères” M.Fontanille, Y. Gnanou (publ. Dunod) 2002, page 368.

To form hyperbranched polymers the unsaturations and/or the site Acapable of initiating the chains may be capable of reacting according toa mechanism of controlled free-radical polymerization, for example,according to a process of atom-transfer radical polymerization (ATRP),described, for example, in Macromolecules 2002, 35, pp. 1146-48, Jho J Yand Yoo S H; or else in Polym. Prepr. 1996, 37(2), 413-14; or elseMatyjaszewski “Progress in polymer science” 26 (3), 337-77, 2001, Annex2.2; Chem. review 2001, 101/12,3737; Mueller “Macromolecules” 34/18,62026-13, 2001.

Generally speaking, atom-transfer free-radical polymerization takesplace by polymerization of at least one free-radically polymerizablemonomers in the presence:

-   of an initiator having at least one transferable halogen atom,-   of a compound comprising a transition metal capable of participating    in a reduction step with the initiator and a “dormant” polymeric    chain;-   and of a ligand selectable from compounds comprising a nitrogen (N),    oxygen (O), phosphorus (P) or sulphur (S) atom and capable of    undergoing coordination via a bond to said compound comprising a    transition metal.

This process is described, for example, in PCT Application No. WO97/18247 and in the article by Matyjasezwski et al. published in JACS,117, page 5641 (1995). The halogen atom is, for example, a chlorine orbromine atom.

In this case, the site A capable of initiating the chains will be ableto be, for example, R1-Cl, with R1 chosen from benzene and OCOCH(CH₃)—.

Among the other processes which can be used non-limiting mention may bemade of the nitroxides method, described for example in Chem. review2001, 101(12), p. 3681. The technique of free-radical polymerization byreaction with a nitroxide consists in blocking the growing free-radicalspecies in the form of a bond of type C—O NR1R2, wherein R1 and R2,which may be identical or different, are each chosen from alkyl radicalshaving 2 to 30 carbon atoms, or together forming, with the nitrogenatom, a ring having 4 to 20 carbon atoms, such as a2,2,6,6-tetramethylpiperidinyl ring, for example.

This polymerization technique is described, for example, in the articles“Synthesis of nitroxy-functionalized polybutadiene by anionicpolymerization using a nitroxy-functionalized terminator”, published inMacromolecules 1997, volume 30, pp. 4238-42, and “Macromolecularengineering via living free radical polymerizations”, published inMacromol. Chem. Phys. 1998, vol. 199, pp. 923-35, or else in PCTApplication No. WO-A-99/03894.

In this case, the site A capable of initiating the chains will be ableto be, for example, of formula:

It is also possible to employ the anionic polymerization methoddescribed for example in Chem. Review 2001, 101/12, p. 3787, and alsothe cationic polymerization method described for example by Charleux etal. in Advances in Polymer Science 142, pp. 1-69, 1999.

The copolymers according to the disclosure have the advantage of beingreadily employable in organic cosmetic media, for example, those of oilyor lipophilic solvent type, while retaining advantageous rheologicalproperties.

The copolymers may be present in the cosmetic or pharmaceuticalcompositions, for example, topical dermatological compositions, in anamount of 0.1% to 95% by weight, for example, 0.5% to 90% by weight, forexample, 1% to 80% by weight, for example, 5%-70% by weight, relative tothe total weight of the composition.

The copolymers may be present in the composition in dissolved form, forexample in a cosmetic organic solvent or a cosmetic oil. Indeed it hasbeen noted that the copolymers according to the disclosure may besoluble therein and that they can be employed therein while retainingadvantageous rheological properties.

The cosmetic or pharmaceutical compositions, for example, dermatologicalcompositions, according to the disclosure comprise, in addition to saidcopolymers, a physiologically acceptable medium, for example, acosmetically or dermatologically acceptable medium, in other words amedium which is compatible with keratin materials such as the skin ofthe face or body, lips, hair, eyelashes, eyebrows and nails.

The composition may, for example, comprise a solvent medium, which maybe a fatty phase, which may itself comprise oils and/or solvents, whichare, for example, lipophilic, and also fatty substances which are solidat ambient temperature, such as waxes, pasty fatty substances, gums, andalso mixtures thereof.

Among the constituents of the fatty phase, non-limiting mention may bemade of oils and/or solvents having an overall solubility parameteraccording to the Hansen solubility space of less than or equal to 20(MPa)^(1/2), for example, less than or equal to 18 (MPa)^(1/2), further,for example, less than or equal to 17 (MPa)^(1/2).

The overall solubility parameter δ according to the Hansen solubilityspace is defined in the article “Solubility parameter values” by EricGrulke in the work “Polymer Handbook”, 3rd edition, chapter VII, pp.519-59 by the following relationship:δ=(dD²+dP²+dH²)^(1/2)wherein:

-   dD characterizes the London dispersion forces resulting from the    formation of dipoles induced during molecular impacts,-   dP characterizes the Debye interaction forces between permanent    dipoles, and-   dH characterizes the specific interaction forces (of hydrogen bond,    acid/base, donor/acceptor type, etc.).

The definition of solvents in the Hansen solubility space is describedin the article by C. M. Hansen “The three dimensional solubilityparameters”, J. Paint Technol. 39, 105 (1967).

Among oils and/or solvents having an overall solubility parameteraccording to the Hansen solubility space of less than or equal to 20(MPa)^(1/2), non-limiting mention may be made of oils, volatile ornon-volatile, which may be selected from natural or synthetic, carbon,hydrocarbon and fluoro oils, optionally branched, alone or in a mixture;ethers and esters having more than 6 carbon atoms, for example, 6 to 30carbon atoms; ketones having more than 6 carbon atoms, for example, 6 to30 carbon atoms; and aliphatic fatty monoalcohols having 6 to 30 carbonatoms, the hydrocarbon chain comprising no substituent group.

As used herein, “non-volatile oil” means an oil capable of remaining onthe skin at ambient temperature and atmospheric pressure for at leastone hour and for example, having a non-zero vapour pressure, at ambienttemperature (25° C.) and atmospheric pressure, of less than 0.01 mmHg(1.33 Pa).

Non-limiting mention may be made, for example, of non-volatile carbonoils, for example, hydrocarbon oils, of plant, mineral, animal orsynthetic origin, such as liquid paraffin (or vaseline), squalane,hydrogenated polyisobutylene (Parleam oil), perhydrosqualene, mink oil,macadamia oil, turtle oil, soya oil, sweet almond oil, calophyllum oil,palm oil, grapeseed oil, sesame oil, corn oil, arara oil, rapeseed oil,sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil,jojoba oil, olive oil or cereal germ oil, or karite butter; linear,branched or cyclic esters having more than 6 carbon atoms, for example,6 to 30 carbon atoms, such as esters of lanolic acid, of oleic acid, oflauric acid and of stearic acid; esters derived from long-chain alcoholsor acids (i.e. those having 6 to 20 carbon atoms), for example, theesters of formula RCOOR′ wherein R is chosen from the residue of ahigher fatty acid comprising 7 to 19 carbon atoms and R′ is chosen froma hydrocarbon chain comprising 3 to 20 carbon atoms, for example,C₁₂-C₃₆ esters, such as isopropyl myristate, isopropyl palmitate, butylstearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate,2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate,2-octyldodecyl myristate or lactate, di(2-ethylhexyl) succinate,diisostearyl malate, glycerol triisostearate or diglyceroltriisostearate; higher fatty acids, for example, C₁₄-C₂₂ acids, such asmyristic acid, palmitic acid, stearic acid, behenic acid, oleic acid,linoleic acid, linolenic acid or isostearic acid; higher fatty alcohols,for example, C₁₆-C₂₂ alcohols, such as cetanol, oleyl alcohol, linoleylalcohol or linolenyl alcohol, isostearyl alcohol or octyldodecanol; andmixtures thereof.

Non-limiting mention may also be made of decanol, dodecanol,octadecanol, the liquid triglycerides of fatty acids of 4 to 10 carbonatoms, such as the triglycerides of heptanoic or octanoic acid, thetriglycerides of caprylic/capric acids; linear or branched hydrocarbonsof mineral or synthetic origin, such as liquid paraffins and derivativesthereof, vaseline, polydecenes, hydrogenated polyisobutene such asParleam; synthetic esters and ethers, for example, those of fatty acids,such as, for example, Purcellin oil, isopropyl myristate, 2-ethylhexylpalmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearylisostearate; hydroxy esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate,triisocetyl citrate, and heptanoates, octanoates and decanoates of fattyalcohols; polyol esters such as propylene glycol dioctanoate, neopentylglycol diheptanoate, diethylene glycol diisononanoate; and esters ofpentaerythritol; fatty alcohols having 12 to 26 carbon atoms such asoctyldodecanol, 2-butyloctanol, 2-hexyldecanol and2-undecylpentadecanol.

Non-limiting mention may also be made of ketones which are liquid atambient temperature, such as methyl ethyl ketone, methyl isobutylketone, diisobutyl ketone, isophorone, cyclohexanone and acetone;propylene glycol ethers which are liquid at ambient temperature, such aspropylene glycol monomethyl ether, propylene glycol monomethyl etheracetate, and dipropylene glycol mono-n-butyl ether; short-chain esters(having 3 to 8 carbon atoms in total) such as ethyl acetate, methylacetate, propyl acetate, n-butyl acetate, and isopentyl acetate; etherswhich are liquid at ambient temperature, such as diethyl ether, dimethylether or dichlorodiethyl ether; alkanes which are liquid at ambienttemperature, such as decane, heptane, dodecane, isododecane,isohexadecane and cyclohexane; cyclic aromatic compounds which areliquid at ambient temperature, such as toluene and xylene; aldehydeswhich are liquid at ambient temperature, such as benzaldehyde andacetaldehyde, and mixtures thereof.

Among the volatile compounds non-limiting mention may be made ofvolatile non-silicone oils, for example, C₈-C₁₆ isoparaffins such asisododecane, isodecane, isohexadecane and, for example, the oils soldunder the trade names Isopar and Permethyl, and for example, isododecane(Permethyl 99 A).

Non-limiting mention may be made of volatile or non-volatile alkaneswhich are liquid at ambient temperature, and, for example, decane,heptane, dodecane, isododecane, isohexadecane, cyclohexane, isodecane,and mixtures thereof.

These oils and/or solvents may be present in an amount ranging from0.01% to 95%, for example, from 0.1% to 90%, further, for example, from10% to 85% by weight, relative to the total weight of the composition,and even further, for example, from 30% to 80%.

The composition may further comprise a hydrophilic medium comprisingwater or a mixture of water and at least one hydrophilic organicsolvents such as alcohols, and for example, lower linear or branchedmonoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol orn-propanol, and polyols such as glycerol, diglycerol, propylene glycol,sorbitol, pentylene glycol, and polyethylene glycols, or elsehydrophilic C₂-C₄ aldehydes and C₂ ethers.

The water or mixture of water and hydrophilic organic solvents may bepresent in the composition according to the disclosure in an amountranging from 0.1% to 80% by weight, relative to the total weight of thecomposition, and, for example, from 1% to 70% by weight.

The composition according to the disclosure may also comprise waxesand/or gums.

As used herein, “wax” means a lipophilic compound which is solid atambient temperature (25° C.), exhibits a reversible solid/liquid statechange, and has a melting point which is greater than or equal to 30° C.and may range up to 120° C. By converting the wax to the liquid state(melting) it is possible to make it miscible with the oils that areoptionally present and to form a microscopically homogeneous mixture,but by taking the temperature of the mixture to ambient temperature thewax recrystallizes in the oils of the mixture. The melting point of thewax may be measured by means of a differential scanning calorimeter(DSC), for example the calorimeter sold under the name DSC 30 byMettler.

The waxes may be hydrocarbon, fluoro and/or silicone waxes and may beplant, mineral, animal and/or synthetic in origin. For example, thewaxes may exhibit a melting temperature greater than 25° C., forexample, greater than 45° C. As a wax which can be used in thecomposition of the disclosure non-limiting mention may be made ofbeeswax, carnauba wax or candelilla wax, paraffin, microcrystallinewaxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxesor Fischer-Tropsch waxes, and silicone waxes such as alkyl- oralkoxy-dimethicones having 16 to 45 carbon atoms.

The gums may be polydimethylsiloxanes (PDMS) of high molecular weight orcellulose gums or polysaccharides, and the pasty substances may behydrocarbon compounds such as lanolins and derivatives thereof or elsePDMS.

The nature and amount of the solids are a function of the desiredmechanical properties and textures. By way of indication, thecomposition may comprise from 0.01% to 50% by weight of waxes, relativeto the total weight of the composition, for example, from 1% to 30% byweight.

The composition according to the disclosure may further comprise atleast one colorant selected from water-soluble dyes, fat-soluble dyes,and pulverulent colorants such as pigments, nacres and flakes which arewell known to the skilled person. Within the composition the colorantsmay be present in an amount ranging from 0.01% to 50% by weight,relative to the weight of the composition, for example, from 0.01% to30% by weight.

By pigments are meant mineral or organic, white or colored particles ofany shape which are insoluble in the physiological medium and areintended for coloring the composition. By nacres are meant iridescentparticles of any shape, for example, those produced by certain molluscsin their shell, or else synthesized. The pigments may be white orcolored, mineral and/or organic. Among mineral pigments non-limitingmention may be made of titanium dioxide, optionally surface-treated,zirconium oxide or cerium oxide, and also zinc oxide, iron oxides(black, yellow or red) or chromium oxide, manganese violet, ultramarineblue, chromium hydrate and ferric blue, and metal powders such asaluminium powder and copper powder. Among organic pigments non-limitingmention may be made of carbon black, D & C pigments, and lakes based oncochineal carmine, barium, strontium, calcium or aluminium. The nacreouspigments may be selected from white nacreous pigments such astitanium-coated mica or bismuth oxychloride, colored nacreous pigmentssuch as titanium mica coated with iron oxides, titanium mica coatedwith, for example, ferric blue or chromium oxide, titanium mica coatedwith an organic pigment of the aforementioned type, and nacreouspigments based on bismuth oxychloride.

Among water-soluble dyes non-limiting mention may be made of thedisodium salt of ponceau, the disodium salt of alizarin green, quinolineyellow, the trisodium. salt of amaranth, the disodium salt oftartrazine, the monosodium salt of rhodamine, the disodium salt offuchsin, xanthophyll and methylene blue.

The composition according to the disclosure may further comprise atleast one filler, for example, in an amount ranging from 0.01% to 50% byweight, relative to the total weight of the composition, for example,ranging from 0.01% to 30% by weight. By fillers are meant particles ofany shape, colorless or white, mineral or synthetic, which are insolublein the medium of the composition irrespective of the temperature atwhich the composition is manufactured. These fillers serve, for example,to modify the rheology or texture of the composition. The fillers may bemineral or organic and of any shape—platelet-like, spherical or oblong,irrespective of the crystallographic form (for example sheet, cubic,hexagonal, orthorhombic, etc.). Non-limiting mention may be made oftalc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® fromAtochem), poly-β-alanine powder and polyethylene powder, powders oftetrafluoroethylene polymers (Teflon®), lauroyllysine, starch, boronnitride, hollow polymeric microspheres such as those of polyvinylidenechloride/acrylonitrile, for instance Expancel® (Nobel Industries) and ofacrylic acid copolymers (Polytrap® from Dow Corning), and silicone resinmicrobeads (Tospearls® from Toshiba, for example), particles ofelastomeric polyorganosiloxanes, precipitated calcium carbonate,magnesium carbonate and hydrogen carbonate, hydroxyapatite, hollowsilica microspheres (Silica Beads® from Maprecos), glass or ceramicmicrocapsules, metal soaps derived from organic carboxylic acids having8 to 22 carbon atoms, for example, 12 to 18 carbon atoms, for examplezinc stearate, magnesium stearate or lithium stearate, zinc laurate ormagnesium myristate.

The composition may further comprise an additional polymer such as afilm-forming polymer. As used herein, “film-forming polymer” means apolymer capable of forming, by itself or in the presence of afilm-forming auxiliary, a continuous film which adheres to a substrate,for example, to keratin materials. Among the film-forming polymers whichcan be used in the composition of the present disclosure non-limitingmention may be made of synthetic polymers, of free-radical orpolycondensate type, polymers of natural origin, and mixtures thereof,for example, acrylic polymers, polyurethanes, polyesters, polyamides,polyureas and cellulosic polymers such as nitrocellulose.

The composition according to the disclosure may also compriseingredients commonly used in cosmetology, such as vitamins, thickeners,gelling agents, trace elements, softeners, sequestrants, perfumes,alkalifying or acidifying agents, preservatives, sunscreens,surfactants, antioxidants, anti-hair-loss agents, anti-dandruff agents,propellants, ceramides, or mixtures thereof. It will be appreciated thatthe person skilled in the art will take care to select this or theseoptional complementary compounds, and/or their amount, in such as waythat the advantageous properties of the composition according to thedisclosure are not, or not substantially, adversely affected by theaddition envisaged.

The composition according to the disclosure may take the form, forexample, of a suspension, a dispersion, a solution, for example, anorganic solution, a gel, an emulsion, for example, an oil-in-water (O/W)or water-in-oil (W/O) emulsion or multiple (W/O/W or polyol/O/W orO/W/O) emulsion, or the form of a cream, a paste, a mousse, a vesicledispersion, for example, of ionic or nonionic lipids, a two-phase ormulti-phase lotion, a spray, a powder, a paste, for example, a flexiblepaste (in particular a paste having a dynamic viscosity at 25° C. of theorder of 0.1 to 40 Pa.s at a shear rate of 200 s⁻¹, after 10 minutes ofmeasurement in cone/plate geometry). The composition may be anhydrous:it may be an anhydrous paste.

The skilled person will be able to select the appropriate presentationform, and the method of preparing it, on the basis of his or her generalknowledge, taking into account on the one hand the nature of theconstituents used, and for example, their solubility in the vehicle, andon the other hand the application envisaged for the composition.

The composition according to the disclosure may be a makeup composition,for example, a complexion product such as a foundation, blusher oreyeshadow; a lip product such as a lipstick or lip care product; aconcealer product; a blusher, mascara or eyeliner; an eyebrow makeupproduct, a lip pencil or eye pencil; a product for the nails such as anail varnish or nail care product; a body makeup product; or a hairmakeup product (mascara or lacquer for hair).

The composition according to the disclosure may be a composition forprotecting or caring for the skin of the face, neck, hands or body, forexample, an anti-Wrinkle composition or anti-fatigue compositionallowing a glow to be imparted to the skin, or a moisturizing ortreatment composition; or an anti-sun or artificial tanning composition.

The composition according to the disclosure may also be a hair product,for example, for holding the hairstyle or shaping the hair. Haircompositions are, for example, shampoos, gels, setting lotions, stylinglotions, fixing compositions and styling compositions such a lacquers orsprays. The lotions may be packaged in various forms, for example, inspray dispensers, pump flasks or aerosol containers, so as to providefor application of the composition in vaporized form or in foam form.Packaging forms of this kind are indicated, for example, when the desireis to obtain a spray or a mousse for fixing or treating the hair.

For example, the composition according to the disclosure may be a makeupcomposition, for example, a foundation or a lipstick.

Disclosed herein is a cosmetic method of making up or caring for keratinmaterials, for example, the skin of the body or the face, the lips, thenails, the hair and/or the eyelashes, comprising applying to saidmaterials a cosmetic composition as defined above.

Disclosed herein is a cosmetic method of making up the skin of the faceand/or the lips, comprising applying to said materials a cosmeticfoundation or lipstick composition as defined above.

Other than in the examples, or where otherwise indicated, all numbersexpressing quantities of ingredients, reaction conditions, and so forthused in the specification and claims are to be understood as beingmodified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by theembodiments disclosed herein. At the very least, and not as an attemptto limit the application of the doctrine of equivalents to the scope ofthe claims, each numerical parameter should be construed in light of thenumber of significant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosed embodiments are approximations, unlessotherwise indicated the numerical values set forth in the specificexamples are reported as precisely as possible. Any numerical value,however, inherently contain certain errors necessarily resulting fromthe standard deviation found in their respective testing measurements.

The embodiments disclosed herein are illustrated in greater detail bythe examples described below.

Method of Determining the Dynamic Storage Modulus E′

The dynamic storage modulus E′ is determined by DMTA (Dynamic andMechanical Temperature Analysis).

To measure E′, viscoelasticimetry tests are performed using a DMTAinstrument from TA Instruments (model DMA2980) on a polymer film sampleapproximately 250±50 μm thick, 5 mm wide and 10 mm long, after drying at23° C. and 50-55% relative humidity for 4 days. This sample is subjectedto a tensile stress. The sample undergoes a weak static force (≅0.1 N)superposed on which there is a sinusoidal displacement of ±8 μm at thefrequency of 1 Hz. Hence operation takes place in the linear field, atlow levels of deformation. This tensile stress is carried out on thesample at temperatures varying from −150° C. to +200° C., with atemperature change of 3° C. per minute.

Using the DMA, a measurement is then made of the complex modulusE*=E′+iE of the polymer tested (where E′ is chosen from the dynamicstorage modulus and E is chosen from the dynamic loss modulus).

The value of the complex modulus at 22° C. is used to deduce the dynamicstorage modulus E′ at a frequency of 1 Hz.

EXAMPLE 1

A 500-ml reactor with central stirring, nitrogen inlet, thermometer andcondenser was charged with 75 g of heptane and heated to 90° C.

The following were then introduced:

-   feed stream 1: 35 g of isobornyl acrylate, 34 g of isobornyl    methacrylate and 1 g of allyl methacrylate, over 1 hour;-   feedstream 2: 1 g of Trigonox 21S and 25 g of heptane, over 48    hours.

When feedstream 1 had finished, feedstream 3 was introduced, comprising30 g of 2-ethylhexyl acrylate, over 2 hours.

Heating was maintained constantly at 90° C. After the end of feedstream2 the system was left at the reflux of the solvent for 3 hours.

120 g of isododecane were added and then the heptane was distilled offunder reduced pressure to give a solution of the polymer in isododecanewith a solids content of 51%.

-   Glass transition temperature: 10° C.-   Measurement of the modulus E′=64±3 MPa

EXAMPLE 2

An anhydrous foundation was prepared, comprising (% by weight):polyethylene wax 12% volatile silicone oils 25% phenyl trimethicone 20%polymethyl methacrylate microspheres 12% solution of the polymer fromExample 1 at 51% solids in isododecane 12% isododecane qs 100%

The waxes were melted and then, when the whole is clear, the phenyltrimethicone was added with stirring, and the silicone oils; thereafterthe microspheres, isododecane and polymer were added. The mixture washomogenized for 15 minutes and then the resulting composition was castand left to cool. This gave an anhydrous foundation.

EXAMPLE 3

A lipstick was prepared, comprising: polyethylene wax 15% solution ofthe polymer from Example 1 at 51% solids in isododecane 20% hydrogenatedpolyisobutene (Parleam from Nippon Oil Fats) 25% pigments 10%isododecane qs 100%

The composition obtained following application to the lips exhibitedgood cosmetic properties.

EXAMPLE 4

A foundation composition was prepared, comprising (% by weight): Phase Acetyl dimethicone copolyol (Abil EM 90 from Goldschmidt) 3 g isostearyldiglyceryl succinate (Imwitor 780K from Condea) 0.6 g pigments (ironoxides and titanium oxide) 10 g polyamide powder (Nylon-12) 8 g solutionof the polymer from Example 1 at 51% solids in isododecane 17 g perfumeqs isododecane 10 g Phase B magnesium sulphate 0.7 g preservative qswater qs 100 g

The composition obtained exhibited good cosmetic properties.

1. A hyperbranched copolymer comprising at least two polymeric branches,which may be identical or different, each comprising at least one atleast trifunctional branch point, wherein a first polymeric branchcomprises at least one first monomer chosen from isobornyl acrylate,isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and2-ethylhexyl acrylate, and a second polymeric branch comprises at leastone second monomer chosen from isobornyl acrylate, isobornylmethacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexylacrylate.
 2. A hyperbranched copolymer according to claim 1, wherein theat least two polymeric branches are connected to one another by apolyfunctional compound comprising at least two polymerizable functionalgroups.
 3. A hyperbranched copolymer according to claim 2, wherein thepolyfunctional compound is chosen from compounds of formula (I):

wherein: R_(a) and R_(c), which may be identical or different, are eachchosen from hydrogen and linear or branched alkyl radicals having 1 to22 carbon atoms. R_(b) is chosen from linear or branched divalentalkylene groups having 1 to 22 carbon atoms, divalent cycloalkylenegroups having 3 to 6 carbon atoms, divalent arylene groups having 6 to18 carbon atoms, and divalent alkarylene groups having 7 to 24 carbonatoms; m and n, which may be identical or different, are each chosenfrom 1, 2, 3 or
 4. 4. A hyperbranched copolymer according to claim 3,wherein R_(a) is a hydrogen atom.
 5. A hyperbranched copolymer accordingto claim 3, wherein R_(c) is a methyl radical.
 6. A hyperbranchedcopolymer according to claim 3, wherein R_(b) is a methylene group.
 7. Ahyperbranched copolymer according to claim 3, wherein the polyfunctionalcompound is chosen from allyl (meth)acrylates.
 8. A hyperbranchedcopolymer according to claim 1, wherein each polymeric branch is in theform of a polymeric sequence of homopolymer type or of random,alternating, block or gradient copolymer type.
 9. A hyperbranchedcopolymer according to claim 1, wherein each polymeric branch is in theform of a linear random copolymer or homopolymer.
 10. A hyperbranchedcopolymer according to claim 1, wherein the main branch is in the formof a homopolymer or a random copolymer comprising 80% to 100% by weight,relative to the weight of the main branch, of at least one monomerchosen from isobornyl acrylate, isobornyl methacrylate, isobutylacrylate, isobutyl methacrylate and 2-ethylhexyl acrylate; and/or thesecondary branch is in the form of a homopolymer or a random copolymercomprising 80% to 100% by weight, relative to the weight of the branch,of at least one monomer chosen from isobornyl acrylate, isobornylmethacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexylacrylate.
 11. A hyperbranched copolymer according to claim 1, whereinthe total amount, in the hyperbranched copolymer, of monomers chosenfrom isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate,isobutyl methacrylate and 2-ethylhexyl acrylate ranges from 50% to 100%by weight, relative to the total weight of monomers present in thehyperbranched copolymer.
 12. A hyperbranched copolymer according toclaim 1, comprising 25% to 75% by weight of the first monomer, which ispresent in the first branch, and 25% to 75% by weight of the secondmonomer, which may be present in the same branch or in another branch,wherein the percentages are relative to the total weight of monomerspresent in the hyperbranched copolymer.
 13. A hyperbranched copolymeraccording to claim 1, comprising a third monomer chosen from isobornylacrylate, isobornyl methacrylate, isobutyl acrylate, isobutylmethacrylate and 2-ethylhexyl acrylate present in an amount ranging from1% to 40% by weight, relative to the weight of the hyperbranchedcopolymer.
 14. A hyperbranched copolymer according to claim 1,comprising, in the same branch or in different branches, the monomercombinations chosen from: isobornyl acrylate and isobornyl methacrylate;isobornyl acrylate and isobutyl acrylate; isobornyl acrylate andisobutyl methacrylate; isobornyl acrylate and 2-ethylhexyl acrylate;isobornyl methacrylate and isobutyl acrylate; isobornyl methacrylate andisobutyl methacrylate; isobornyl methacrylate and 2-ethylhexyl acrylate;isobornyl acrylate, isobornyl methacrylate and 2-ethylhexyl acrylate;isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate;isobornyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate;isobornyl acrylate, isobutyl methacrylate and isobutyl acrylate; andisobornyl methacrylate, isobutyl methacrylate and isobutyl acrylate. 15.A hyperbranched copolymer according to claim 1, comprising monomercombinations chosen from: isobornyl acrylate in the main branches andisobutyl acrylate in the secondary branches; isobornyl acrylate in themain branches and 2-ethylhexyl acrylate in the secondary branches;isobornyl methacrylate in the main branches and isobutyl acrylate in thesecondary branches; isobornyl methacrylate in the main branches and2-ethylhexyl acrylate in the secondary branches; isobornyl acrylate andisobornyl methacrylate in the main branches and isobutyl acrylate in thesecondary branches; isobornyl acrylate and isobornyl methacrylate in themain branches and 2-ethylhexyl acrylate in the secondary branches;isobornyl acrylate and isobutyl methacrylate in the main branches andisobutyl acrylate in the secondary branches; isobornyl acrylate andisobutyl methacrylate in the main branches and 2-ethylhexyl acrylate inthe secondary branches; isobornyl methacrylate and isobutyl methacrylatein the main branches and isobutyl acrylate in the secondary branches;and isobornyl methacrylate and isobutyl methacrylate in the mainbranches and 2-ethylhexyl acrylate in the secondary branches.
 16. Ahyperbranched copolymer according to claim 1, further comprising atleast one additional monomer, which may be present in an amount rangingfrom 0% to 50% by weight, relative to the total weight of monomerspresent in the hyperbranched copolymer.
 17. A hyperbranched copolymeraccording to claim 16, wherein the at least one additional monomer ischosen from the following monomers, and the salts thereof: (i)(meth)acrylates of formula CH₂═CHCOOR or CH₂═C(CH₃)COOR wherein R ischosen from: a linear or branched alkyl groups comprising from 1 to 30carbon atoms, wherein said alkyl is intercalated with at least oneheteroatom selected from O, N, S and P, and/or wherein said alkyl groupis optionally substituted by at least one substituent selected from OH,halogen atoms, NR4R5, wherein R4 and R5, which may be identical ordifferent, are chosen from hydrogen, C₁ to C₆ linear or branched alkylgroups, and phenyl groups; and polyoxyalkylene groups comprising therepetition of 5 to 30 oxyalkylene units; a C₃ to C₁₂ cycloalkyl group,said cycloalkyl group being able to contain, in its chain, at least oneheteroatom chosen from O, N, S and P, and/or to be optionallysubstituted by at least one substituent selected from —OH and halogenatoms; and a C₄ to C₂₀ aryl or C₅ to C₃₀ aralkyl group (with a C₁ to C₈alkyl group); (ii) (meth)acrylamides chosen from CH₂═CHCONR4R5 andCH₂═C(CH₃)CONR4R5 wherein R4 and R5, which may be identical ordifferent, are chosen from a) a hydrogen atom; b) a linear or branchedalkyl group comprising from 1 to 18 carbon atoms, wherein said alkyl isoptionally intercalated with at least one heteroatom selected from O, N,S and P; wherein said alkyl group is optionally substituted by at leastone substituent selected from hydroxyl groups, halogen atoms andSi(R4R5), wherein R4 and R5, which are identical or different, arechosen from C₁ to C₆ alkyl groups and phenyl groups; c) a C3 to C12cycloalkyl group, or a heterocycloalkyl group, wherein the alkyl has 1to 4 carbon atoms; d) a C4 to C20 aryl group, and e) a C5 to C30 aralkylgroup, with a C1 to C8 alkyl group; (iii) ethylenically unsaturatedmonomers comprising at least one carboxylic, phosphoric or sulphonicacid or anhydride function; (iv) vinyl ethers chosen from R6O—CH═CH₂ andR6-COO—CH═CH₂ wherein R6 is chosen fromlinear or branched alkyl groupscomprising from 1 to 22 carbon atom; cyclic alkyl groups comprising from3 to 6 carbon atoms and aromatic groups; (v) vinyl compounds chosen fromCH₂═CH—R9, CH₂═CH—CH₂—R9 and CH₂═C(CH₃)═CH₂—R9 wherein R9 is chosen fromhydroxyl, chlorine, fluorine, NH₂ groups and OR10 wherein R10 is chosenfrom phenyl groups; C₁ to C₁₂ alkyl groups wherein the monomer is avinyl or allyl ether; acetamide groups (NHCOCH₃); OCOR11 wherein R11 ischosen from alkyl groups comprising from 2 to 12 carbons which is linearor branched, wherein the monomer is a vinyl or allyl ester; linear orbranched alkyl groups of 1 to 18 carbon atoms, wherein said alkyl isoptionally intercalated with at least one heteroatom selected from O, N,S and P, wherein said alkyl group is optionally substituted by at leastone substituent selected from hydroxyl groups, halogen atomsandSi(R4R5), wherein R4 and R5, which may be identical or different, arechosen from C₁ to C₆ alkyl groups and phenyl groups; C₃ to C₁₂cycloalkyls; C₃ to C₂₀ aryl groups; C₄ to C₃₀ aralkyl groups with a C₁to C₈ alkyl group; 4- to 12-membered aromatic or non-aromaticheterocyclic groups comprising at least one heteroatom selected from O,N and S, and heterocycloalkyl groups with a C₁ to C₄ alkyl group; (vi)styrene and its derivatives; and (vii) ethylenically unsaturatedmonomers comprising at least one silicon atoms;
 18. A hyperbranchedcopolymer according to claim 17, wherein R is chosen from methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl,octyl, lauryl, isooctyl, isodecyl, dodecyl, cyclohexyl,t-butylcyclohexyl, stearyl, 2-ethylperfluorohexyl, 2-hydroxyethyl,2-hydroxybutyl, 2-hydroxypropyl, methoxyethyl, ethoxyethyl,methoxypropyl, isobornyl, phenyl, 2-phenylethyl, t-butylbenzyl, benzyl,furfurylmethyl or tetrahydrofurfurylmethyl groups;methoxy-polyoxyethylene (or POE-methyl) groups; POE-behenyl ortrifluoroethyl groups; and a dimethylaminoethyl, diethylaminoethyl ordimethylaminopropyl groups.
 19. A hyperbranched copolymer according toclaim 17, wherein the alkyl of ii) b) is chosen from methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, isohexyl,cyclohexyl, ethylhexyl, octyl, isooctyl, decyl, isodecyl, cyclodecyl,dodecyl, cyclododecyl, isononyl, lauryl, t-butylcyclohexyl or stearylgroups; 2-ethylperfluorohexyl groups; C₁₋₄ hydroxyalkyl groups; and C₁₋₄alkoxy-C₁₋₄ alkyl groups.
 20. A hyperbranched copolymer according toclaim 17, wherein the ethylenically unsaturated monomers comprising atleast one carboxylic, phosphoric or sulphonic acid or anhydride functionare chosen from acrylic acid, methacrylic acid, crotonic acid, maleicanhydride, itaconic acid, fumaric acid, maleic acid, styrenesulphonicacid, vinylbenzoic acid, vinylphosphoric acid oracrylamidopropanesulphonic acid; and the salts thereof;
 21. Ahyperbranched copolymer according to claim 16, wherein the additionalmonomer is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl,t-butyl, cyclohexyl, methoxyethyl, ethoxyethyl, trifluoroethyl,dimethylaminoethyl, diethylaminoethyl, 2-hydroxypropyl and2-hydroxyethyl (meth)acrylates; acrylic acid, methacrylic acid,(meth)acrylamide, methacryloyloxypropyltrimethoxysilane,methacryloyloxypropyltris(trimethylsiloxy)silane; and their salts; andmixtures thereof.
 22. A hyperbranched copolymer according to claim 16,wherein the additional monomer is selected from carbon or siliconemacromonomers having at least one polymerizable end group.
 23. Ahyperbranched copolymer according to claim 16, wherein the additionalmonomer is selected from vinyl and (meth)acrylate groups.
 24. Ahyperbranched copolymer according to claim 22, wherein the macromonomeris chosen from: (i) linear or branched C₈-C₂₂ alkyl (meth)acrylatehomopolymers and copolymers having a polymerizable end group selectedfrom vinyl and (meth)acrylate groups; poly(dodecyl acrylate) orpoly(dodecyl methacrylate) macromonomers having a mono(meth)acrylate endgroup; and poly(stearyl acrylate) or poly(stearyl methacrylate)macromonomers having a mono(meth)acrylate end group, (ii) polyolefinshaving an ethylenically unsaturated end group; and (iii)polydimethylsiloxanes having a mono(meth)acrylate end group.
 25. Ahyperbranched copolymer according to claim 24, wherein the polyolefinshaving an ethylenically unsaturated end group are chosen frompolyethylene macromonomers, polypropylene macromonomers,polyethylene/polypropylene copolymer macromonomers,polyethylene/polybutylene copolymer macromonomers, polyisobutylenemacromonomers; polybutadiene macromonomers; polyisoprene macromonomers;and poly(ethylene/butylene)-polyisoprene macromonomers, wherein themacromonomer has (meth)acrylate end group.
 26. A hyperbranched copolymeraccording to claim 24, wherein the polydimethylsiloxanes having amono(meth)acrylate end group are chosen from compounds of formula (IIa):

wherein: R₈ is chosen from a hydrogen atom and a methyl group; R₉ ischosen from a linear or branched divalent hydrocarbon group having 1 to10 carbon atoms and optionally comprising one or two ether bonds —O—;R₁₀ is chosen from a linear or branched alkyl group having 1 to 10carbon atoms; and n is chosen from an integer ranging from 1 to
 300. 27.A hyperbranched copolymer according to claim 1, comprising at least one“high Tg” branch or polymeric sequence having a Tg greater than or equalto 20° C.
 28. A hyperbranched copolymer according to claim 27, whereinthe at least one “high-Tg” branch is present in an amount greater thanor equal to 50% by weight, relative to the total weight of thehyperbranched copolymer.
 29. A hyperbranched copolymer according toclaim 1, comprising at least one “low-Tg” branch or sequence having a Tgless than 20° C.
 30. A hyperbranched copolymer according to claim 29,wherein the at least one “low-Tg” branch is present in an amount lessthan 50% by weight, relative to the total weight of the hyperbranchedcopolymer.
 31. A hyperbranched copolymer according to claim 27, whereinthe at least one “high-Tg” branch comprises “high-Tg” monomers presentin a proportion of 30% to 100% by weight, relative to the total weightof said at least one “high-Tg” branch.
 32. A hyperbranched copolymeraccording to claim 29, wherein the at least one “low-Tg” branchcomprises low-Tg monomers present in a proportion of 30% to 100% byweight, relative to the total weight of said at least one “low-Tg”branch.
 33. A hyperbranched copolymer according to claim 1, wherein themain branch is “high-Tg” having a Tg greater than or equal to 20° C. andat least one of the secondary branches is “low-Tg” having a Tg less than20° C.
 34. A hyperbranched copolymer according to claim 1, comprising atleast one “high-Tg” monomer having a Tg greater than or equal to 20° C.35. A hyperbranched copolymer according to claim 34, wherein the atleast one “high-Tg” monomer is present in an amount ranging from 40% to100% by weight, relative to the total weight of monomers present in thehyperbranched copolymer.
 36. A hyperbranched copolymer according toclaim 1, comprising at least one “low-Tg” monomer having a Tg less than20° C.
 37. A hyperbranched copolymer according to claim 36, wherein theat least one “low-Tg” monomer is present in an amount ranging from 0 to60% by weight, relative to the total weight of monomers present in thehyperbranched copolymer.
 38. A hyperbranched copolymer according toclaim 1, comprising at least one lipophilic monomer, which is present inan amount ranging from 40% to 100% by weight, relative to the totalweight of monomers present in the hyperbranched copolymer.
 39. Ahyperbranched copolymer according to claim 1, comprising at least onehydrophilic monomer, which is present in an amount ranging from 0% to60% by weight, relative to the total weight of monomers present in thehyperbranched copolymer.
 40. A hyperbranched copolymer according toclaim 1, wherein the main branch is lipophilic.
 41. A hyperbranchedcopolymer according to claim 1, wherein all the branches are lipophilic.42. A hyperbranched copolymer according to claim 1, having anumber-average molecular mass ranging from 2000 g/mol and 1 500 000g/mol.
 43. A hyperbranched copolymer according to claim 1, soluble at aconcentration of at least 3% by weight in isododecane at 25° C. and 1atm.
 44. A hyperbranched copolymer obtainable by a process comprising: afirst step comprising free-radical polymerization in the presence of atleast one polyfunctional compound comprising at least two polymerizablefunctional groups, and a at least one monomer selected from isobornylacrylate, isobornyl methacrylate, isobutyl acrylate, isobutylmethacrylate and 2-ethylhexyl acrylate; and a second step comprising thefree-radical polymerization of at least one monomer selected fromisobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutylmethacrylate and 2-ethylhexyl acrylate, optionally in the presence of apolyfunctional compound.
 45. A hyperbranched copolymer according toclaim 44, wherein the polyfunctional compound corresponds to the formula(I):

wherein: R_(a) and R_(c), which may be identical or different, are eachchosen from hydrogen and linear or branched alkyl radicals having 1 to22 carbon atoms; R_(b) is chosen from a linear or branched divalentalkylene groups having 1 to 22 carbon atoms, divalent cycloalkylenegroups having 3 to 6 carbon atoms, divalent arylene groups having 6 to18 carbon atoms, and divalent alkarylene group having 7 to 24 carbonatoms; m and n, which may be identical or different, are each chosenfrom 1, 2, 3 or
 4. 46. A hyperbranched copolymer according to claim 45,wherein the polyfunctional compound is chosen from allyl(meth)acrylates.
 47. A hyperbranched copolymer according to claim 45,wherein the polyfunctional compound is used in an amount ranging from0.05% to 15% by weight, relative to the total weight of thehyperbranched copolymer.
 48. A cosmetic or pharmaceutical compositioncomprising, in a physiologically acceptable medium, at least onehyperbranched copolymer comprising at least two polymeric branches,which may be identical or different, each comprising at least one atleast trifunctional branch point, wherein a first polymeric branchcomprises at least one first monomer chosen from isobornyl acrylate,isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and2-ethylhexyl acrylate, a second polymeric branch comprises at least onesecond monomer chose from isobornyl acrylate, isobornyl methacrylate,isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate. 49.A composition according to claim 48, wherein the at least onehyperbranched copolymer is present in an amount ranging from 0.1% to 95%by weight, relative to the total weight of the composition.
 50. Acomposition according to claim 48, comprising at least one fatty phasecomprising at least one constituent selected from oils, solvents, andfatty substances which are solid at ambient temperature, and mixturesthereof.
 51. A composition according to claim 50, comprising at leastone constituent selected from oils and/or solvents having an overallsolubility parameter according to the Hansen solubility space of lessthan or equal to 20 (MPa)^(1/2).
 52. A composition according to claim51, wherein the oils and/or solvents having an overall solubilityparameter according to the Hansen solubility space of less than or equalto 20 (MPa)^(1/2) are selected from oils, volatile or non-volatile,which may be selected from natural or synthetic, carbon, hydrocarbon andfluoro oils, optionally branched, alone or in a mixture; ethers andesters having more than 6 carbon atoms; ketones having more than 6carbon atoms; and aliphatic fatty monoalcohols having 6 to 30 carbonatoms, the hydrocarbon chain comprising no substituent group.
 53. Acomposition according to claim 52, wherein the oils and/or solvents areselected from hydrocarbon oils, of plant, mineral, animal or syntheticorigin.
 54. A composition according to claim 53, wherein the hydrocarbonoils are selected from liquid paraffin (or vaseline), squalane,hydrogenated polyisobutylene (Parleam oil), perhydrosqualene, mink oil,macadamia oil, turtle oil, soya oil, sweet almond oil, calophyllum oil,palm oil, grapeseed oil, sesame oil, corn oil, arara oil, rapeseed oil,sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil,jojoba oil, olive oil or cereal germ oil, or karite butter; linear,branched or cyclic esters having more than 6 carbon atoms; estersderived from long-chain alcohols or acids; esters of formula RCOOR′wherein R is chosen from the residue of a higher fatty acid comprising 7to 19 carbon atoms and R′ is chosen from a hydrocarbon chain comprising3 to 20 carbon atoms; higher fatty acids; C₁₄-C₂₂ fatty acids chosenfrom myristic acid, palmitic acid, stearic acid, behenic acid, oleicacid, linoleic acid, linolenic acid or isostearic acid; higher fattyalcohols; C₁₆-C₂₂ fatty alcohols chosen from cetanol, oleyl alcohol,linoleyl alcohol or linolenyl alcohol, isostearyl alcohol oroctyldodecanol; and mixtures thereof; decanol, dodecanol, octadecanol,the liquid triglycerides of fatty acids of 4 to 10 carbon atoms; linearor branched hydrocarbons of mineral or synthetic origin; syntheticesters and ethers; hydroxy esters; polyol esters; and esters ofpentaerythritol; fatty alcohols having 12 to 26 carbon atoms; ketoneswhich are liquid at ambient temperature; propylene glycol ethers whichare liquid at ambient temperature; short-chain esters having 3 to 8carbon atoms; ethers which are liquid at ambient temperature; alkaneswhich are liquid at ambient temperature; cyclic aromatic compounds whichare liquid at ambient temperature; aldehydes which are liquid at ambienttemperature; and volatile non-silicone oils.
 55. A composition accordingto claim 48, comprising at least one oil and/or solvent selected fromvolatile or non-volatile alkanes which are liquid at ambienttemperature.
 56. A composition according to one claim 55, wherein the atleast one oil and[or solvent is present in an amount ranging from 0.01%to 95% by weight, relative to the total weight of the composition.
 57. Acomposition according to claim 48, further comprising a constituentselected from a hydrophilic medium comprising water or a mixture ofwater and hydrophilic organic solvent; waxes, gums; colorants; fillers;polymers; vitamins, thickeners, gelling agents, trace elements,softeners, sequestrants, perfumes, alkalifying or acidifying agents,preservatives, sunscreens, surfactants, antioxidants, anti-hair-lossagents, anti-dandruff agents, propellants, ceramides, or mixturesthereof.
 58. A composition according to claim 48, in the form of asuspension, a dispersion, a solution, a gel, an emulsion, a cream, apaste, a mousse, a vesicle dispersion, a two-phase or multi-phaselotion, a spray, a powder, a paste, or in anhydrous form.
 59. Acomposition according to claim 48, in the form of a makeup compositionchosen from a foundation, blusher or eyeshadow; a lip product; aconcealer product; a blusher, mascara or eyeliner; an eyebrow makeupproduct, a lip pencil or eye pencil; a product for the nails; a bodymakeup product; a hair makeup product; in the form of a composition forprotecting or caring for the skin of the face, neck, hands or body; amoisturizing or-treatment composition; or an anti-sun or artificialtanning composition; or a hair composition.
 60. A composition accordingto claim 59, wherein the makeup composition is chosen from a foundationand a lipstick.
 61. A cosmetic method of making up or caring for keratinmaterials comprising applying to said materials a cosmetic orpharmaceutical composition comprising, in a physiologically acceptablemedium, at least one hyperbranched copolymer comprising at least twopolymeric branches, which may be identical or different, each comprisingat least one at least trifunctional branch point, wherein a firstpolymeric branch comprises at least one first monomer chosen fromisobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutylmethacrylate and 2-ethylhexyl acrylate, a second polymeric branchcomprises at least one second monomer chose from isobornyl acrylate,isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and2-ethylhexyl acrylate.
 62. A cosmetic method of making up the skin ofthe face and/or the lips, comprising applying to said materials acosmetic foundation or lipstick composition comprising a cosmetic orpharmaceutical composition comprising, in a physiologically acceptablemedium, at least one hyperbranched copolymer comprising at least twopolymeric branches, which may be identical or different, each comprisingat least one at least trifunctional branch point, wherein a firstpolymeric branch comprises at least one first monomer chosen fromisobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutylmethacrylate and 2-ethylhexyl acrylate, a second polymeric branchcomprises at least one second monomer chose from isobornyl acrylate,isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and2-ethylhexyl acrylate.